Sodium methanethiolate → 4-Methoxy-1-[2-(methylthio)ethyl]-2-nitrobenzene

HRID 1914699

反応式

HRID 1914699 の反応式
Br[CH2:2][CH2:3][C:4]1[CH:9]=[CH:8][C:7]([O:10][CH3:11])=[CH:6][C:5]=1[N+:12]([O-:14])=[O:13].[CH3:15][S-:16].[Na+]>CCO>[CH3:11][O:10][C:7]1[CH:8]=[CH:9][C:4]([CH2:3][CH2:2][S:16][CH3:15])=[C:5]([N+:12]([O-:14])=[O:13])[CH:6]=1

参加物

4

反応物 2

HCID 4378561Sodium methanethiolateHCID 593530021-(2-Bromoethyl)-4-methoxy-2-nitrobenzene

生成物 1

HCID 593530214-Methoxy-1-[2-(methylthio)ethyl]-2-nitrobenzene収率 67%

試薬・触媒・溶媒 1

HCID 702Ethanol溶媒

反応条件

温度
25.5 °C

実験手順

A suspension of 1-(2-bromoethyl)-4-methoxy-2-nitrobenzene (14.7 g, 0.06 mol) in EtOH (150 mL) is stirred at 25-26° C. under a nitrogen atmosphere. Sodium thiomethoxide (7.9 g, 0.1 mol) is added in one portion at 25-26° C. and the reaction mixture is heated to reflux for 12 h. The solvent is removed under reduced pressure and the brown residue is taken up in cold water (100 mL). The crude product is extracted with EtOAc (2×200 mL). The organic layer is washed with water and brine (200 mL, each), then dried over Na2SO4 and the solvent is removed under reduced pressure to afford a brown oil. The crude product is purified by column chromatography (60-120 mesh silica gel, eluent 2% EtaAc in petrol ether) to give 8.3 g (67%) of the title compound as light brown liquid. 1H NMR (DMSO-d6, 400 MHz) δ 7.47-7.45 (m, 2H), 7.20-724(m 1H,), 3.81 (s, 3H), 3.01-2.97 (m, 2H), 2.69-2.66 (m, 2H), 2.05 (s, 3H). LC/MS: (ES+) 227.9.

後処理

  1. temperaturethe reaction mixture is heated
  2. temperatureto reflux for 12 h
  3. customThe solvent is removed under reduced pressure
  4. extractionThe crude product is extracted with EtOAc (2×200 mL)
  5. washThe organic layer is washed with water and brine (200 mL
  6. dry with materialeach), then dried over Na2SO4
  7. customthe solvent is removed under reduced pressure
  8. customto afford a brown oil
  9. customThe crude product is purified by column chromatography (60-120 mesh silica gel, eluent 2% EtaAc in petrol ether)

出典と根拠

ORDレコード
ord-0561b52d6756460d813ca35781699c94
出典データセット
uspto-grants-2013_12
特許番号
US08614215B2

関連ノート

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